Four polyoxyethylenated pentaerythritol (PE) ester surfactants have been synthesized. The molecular weights of these surfactants were calculated and evaluated experimentally by GPC and confirmed by calculations based on1H-NMR. Also, their HLB values were calculated by Griffin formula. The surface tension and thermodynamic properties of the surfactants were obtained from surface tension measurements at different temperatures (298–318 K). It was found that the minimum area/surfactant molecule (Amin) for the investigated surfactants increased with increasing the molecular weight of the incorporated ethylene oxide. The thermodynamic parameters of micellization (ΔGmic, ΔHmic and ΔSmic) and that for adsorption (ΔGad, ΔHad and ΔSad) were also calculated. The more negative Gibbs free energy of adsorption values than those of micellization suggest that these surfactants favor adsorption than micellization. This finding is utilized for monitoring their dispersancy power. It was found that the water solubility of the prepared surfactants is correlated to their HLB values. Furthermore, the biodegradability of the prepared compounds was studied at different conditions in order to investigate their usability as oil spill dispersants. The data revealed that PE200-C12 had maximum dispersion efficiency and it was completely biodegraded after 8 days.
From Manar El-Sayed Abdel-Raouf
(Received 13.08.2011; revised 23.09.2011)
Appeared in Tenside Surfactants Detergents 2012/02, Page 114-123
Direct link: http://www.tsd-journal.com/TS110172
Biodegradable Polyoxyethylenated Pentaerythritol Quaternary Esters as Oil Spill Dispersants [618 KB]
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1 Ikada, Y. and Tsuji, H.: Biodegradable polyesters for medical and ecological applications, Macromol. Rapid Commun. 21 (2000) 117– 132.
2 Edlund, U. and Albertsson, A.C.: Polyesters based on diacid monomers, Adv. Drug Deliv. Rev. 55 (2003) 585– 609.
3 Hsin-Cheng, C., Kopekova, P., Sharad, S. and Kopeek, J.: Lysosomal degradability of poly(a-amino acids), J. Biomed. Mater. Res. 34(3) (1997) 381– 392.
4 Wei, M., Chang, J., Yao, K. D., Steven, N. G. and Heller, J.: Drug release from poly(ortho esters)-poly(ethylene glycol) polyblend, J. Appl. Polym. Sci. 71(2) (1999) 303– 309.
5 Domb, J. and Langer, R.: Polyanhydrides: I. Preparation of high molecular weight polyanhydrides, J. Polym. Sci., A, Polym. Chem. 25(12) (1987) 3373– 3386.
6 Huang, S. J. and Kim, S. H.: Poly(amide-esters) from p-amino benzoic acid, Polym. Int. 46 (1998) 172– 176.
7 Tuominen, J. and Seppala, J. V.: Synthesis and characterization of lactic acid based poly (ester-amide), Macromolecules 33 (2000) 3530–3535.
8 Goodman, R. and Vachon, N.: Copolyesteramides-II, anionic copolymers of e-caprolactam with e-caprolactone: preparation and general properties, Eur. Polym. J. 20(6) (1984) 529– 537.
9 Qian, Z. Y., Li, S., He, Y., Zhang, H. L. and Liu, X. B.: Hydrolytic degradation study of biodegradable polyesteramide copolymers based on caprolactone and 11-aminoundecanoic acid, Biomaterials 25 (2004) 1975–1981.
10 Abdul-Raouf, M. E.: Synthesis and Characterization of Some Degradable Polyesters, Material Research Innovation 10(2) (2006) 231–252.
11 Robertson, S. B., Steen, A., Skewes, D. Pavia, R. and Walker, A. H.: Marine oil spill response options: the manual. International Oil Spill Conference Proceedings. API Publication No. 4651, Washington, DC. 1997
12 Strom-Kristiansen, T., Daling, D. S., Brandvik, P. J. and Jensen, H.: Mechanical recovery of chemically treated oil slicks. In Proceedings of the Nineteenth Arctic and Marine Oil Spill Program. Environment Canada, Ottawa, Ontario, Canada, 1996.
13 Cui, Z.: Synthesis of dodecyllauroylbenzenesulfonate and its application in enhanced oil recovery, Tenside Surfactants Detergents 48(5) (2011) 408–414.
14 Iglauer, S., Wu, Y., Shuler, P. J., Tang, Y. and Goddard, W. A.: Alkylpolyglucoside/1-Naphthol Formulations: a case study of surfactant enhanced oil recovery, Tenside Surfactants Detergents 48(2) (2011) 121–126.
15 Iglauer, S., Wu, Y., Shuler, P. J., Tang, Y. and Goddard, W. A.: Alkylpolyglucoside surfactant-sorbitan ester cosurfactant formulations for improved oil recovery, Tenside, Surfactants, Detergents 47(5) (2010) 280–287.
16 Iglauer, S., Wu, Y., Shuler, P. J., Tang, Y. and Goddard, W. A.: Branched alkyl alcohol propoxylate sulfate surfactant-cosolvent formulations for improved oil recovery, Tenside Surfactants Detergents, Vol. 47(3) (2010) 152– 161.
17 Atta, A. M., Abdel-Raouf, M. E., Abdel-Raheim A. M. and Abdel-Azim, A. A.: Surfactants from Recycled Poly (ethylene terephthalate) Waste as Water Based on Oil Spill Dispersants, Journal of Polymer Research 13 (2006) 39–52.
18 El-Saeed, S. M., Farag, R. K., Abdul-Raouf, M. E. and Abdel-Azim, A. A.: Synthesis and Characterization of Novel Crude oil dispersants based on Ethoxylated Schiff base, International J. of Polymeric Materials 57 (2008) 860–877.
19 Major, R. A., Gray, N. R. and Marucci, T. F.: Dispersant application by fire monitor. In 1993 International Oil Spill Conference Proceedings. American Petroleum Institute Publication No. 4580, Washington, DC, 1993.
20 Abdel-Raouf, M. E., Abdel-Raheim A. M. and Abdel-Azim, A. A.: Surface Properties and Thermodynamic Parameters of Some Sugar-Based Ethoxylated Amine Surfactants: 1-Synthesis, Characterization, and Demulsification Efficiency, J. Surfactant and Detergent 14 (2011) 113–121.
21 ASTM D2024-65(2003), Standard test method for cloud point of nonionic surfactants.
22 Fingas, M. F., Stoodley R. and Laroche, N.: Development of A Surface Washing Agent Effectiveness Protocol, Oil Chem. Pollut. 7 (1990) 337.
23 Standard ISO 9408:1999. Evaluation of ultimate aerobic biodegradability of organic compounds in aqueous medium by determination of oxygen demand in a closed respirometer.
24 Nael, N. Z., Abdel-Raheim A. M. and Abdel-Azim, A. A.: Propylene oxide – Ethylene oxide block copolymers as demulsifiers for water-in-oil emulsions. I-Effect of molecular weight and Hydrophilic-lipophilic balance (HLB) on the demulsification efficiency, Monatshefte Für Chemie (Chemical Monthly) of Austria 127 (1996) 621.
25 Griffin, W. C.: Calculation of HLB values of non-ionic surfactants. J. Soc. Cosmet. Chem. 5 (1954) 249–256.
26 Rosen, M. J.: Structure/performance relationships in surfactants. American Chemical Society, Washington, 1984.
27 Rosen, M. J., Cohen, W. A. and Hua, X. Y.: Relationship of structure to properties in surfactants: Surface and thermodynamic properties of 2-dodecyloxypoly (ethenoxyethanol)s, C12H25(OC2H4)xOH, in aqueous solution. J. Phys. Chem. 86 (1982) 541–545.
28 Schick, M. J.: Non-ionic surfactants: physical chemistry, Marcel Dekker, NY, 1987.
29 Robert, J. F. and Lewis, A.: Oil spill dispersants, Pure Appl. Chem. 71(1) (1999), 27–42.
30 Schramm, L. L.: Surfactants: Fundamentals and Applications in the Petroleum Industry, Cambridge University Press, UK, 2000.
31 Esumi, K. and Ueno, M.: Structure-performance relationships in surfactants, Surfactant Science Series, Marcel Dekker Inc., NY, 1997.
32 Connor, P. and Ottewill, R. H.: The Adsorption of Cationic Surface Active Agents on Polystyrene Surfaces, J. Colloid and Interface Sci. 37 (1971) 642–651.
33 Rosen, M. J.: Surfactants and Interfacial Phenomena, 2nd ed., John, Wiley and Sons Inc., New York, 1989.
34 Law, R. J. and Kelly, C.: The Impact of the “Sea Empress” Oil Spill, Aquatic Living Resources 17 (2004), 389–394.
35 Lessard, R. R. and Demarco, G.: The Significance of Oil Spill Dispersants, Spill Science and Technology Bulletin 6 (2000) 59–68.
36 Iglauer, S., Wu, Y., Shuler, P. J., Tang, Y. and Goddard, W. A.: Analysis of the influence of alkyl polyglycoside surfactant and cosolvent structure on interfacial tension in aqueous formulations versus n-octane Tenside Surfactants Detergents 47(2) (2010) 87–97.
37 Fujimoto, T.: New Introduction to Surface Active Agents, Sanyo Chemical Industries, Ltd., 1985.
38 Abdallah, S. Z., Mohamed, M. and Ahmed, F. M.: Effect of Biological and Chemical Dispersants on Oil Spills, Petroleum Science and Technology 23 (2005), 463–474.
39 Sturm, R. N.: Biodegradability of nonionic surfactants: Screening test for predicting rate and ultimate biodegradation, Journal of the American Oil Chemists’ Society 50(5) (2007) 159–167.
40 Mausner, M., Benedict, J. H., Booman, K. A., Brenner, T. E., Conway, R. A., Duthie, J. R., Garrison, L. J., Hendrix, C. D. and Shewmaker, J. E.: The status of biodegradability testing of nonionic surfactants, Journal of the American Oil Chemists’ Society 46(9) (2007) 432–440.
41 Swannell, R. P. J., Daniel, F., Croft, B. C., Engelhardt, M. A., Wilson, S., Mitchell, D. J. and Lunel, T.: Influence of physical and chemical dispersion on the biodegradation of oil under simulated marine conditions. In Proceedings of the 20thArctic and Marine Oil Spill Program. Environment Canada, Ottawa, Ontario, Canada, 1997.
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